Not Applicable
1. Field of the Invention
The present invention relates to a cover for a golf ball. More specifically, the present invention relates to a golf ball cover layer composed of a polyurethane formed from a blend of diisocyanate prepolymers.
2. Description of the Related Art
Conventionally golf balls are made by molding a cover around a core. The core may be wound or solid. A wound core typically comprises elastic thread wound about a solid or liquid center. Unlike wound cores, solid cores do not include a wound elastic thread layer. Solid cores typically may comprise a single solid piece center or a solid center covered by one or more mantle or boundary layers of material.
The cover may be injection molded, compression molded, or cast over the core. Injection molding typically requires a mold having at least one pair of mold cavities, e.g., a first mold cavity and a second mold cavity, which mate to form a spherical recess. In addition, a mold may include more than one mold cavity pair.
In one exemplary injection molding process each mold cavity may also include retractable positioning pins to hold the core in the spherical center of the mold cavity pair. Once the core is positioned in the first mold cavity, the respective second mold cavity is mated to the first to close the mold. A cover material is then injected into the closed mold. The positioning pins are retracted while the cover material is flowable to allow the material to fill in any holes caused by the pins. When the material is at least partially cured, the covered core is removed from the mold.
As with injection molding, compression molds typically include multiple pairs of mold cavities, each pair comprising first and second mold cavities that mate to form a spherical recess. In one exemplary compression molding process, a cover material is pre-formed into half-shells, which are placed into a respective pair of compression mold cavities. The core is placed between the cover material half-shells and the mold is closed. The core and cover combination is then exposed to heat and pressure, which cause the cover half-shells to combine and form a full cover.
As with the above-referenced processes, a casting process also utilizes pairs of mold cavities. In a casting process, a cover material is introduced into a first mold cavity of each pair. Then, a core is held in position (e.g. by an overhanging vacuum or suction apparatus) to contact the cover material in what will be the spherical center of the mold cavity pair. Once the cover material is at least partially cured (e.g., a point where the core will not substantially move), the core is released, the cover material is introduced into a second mold cavity of each pair, and the mold is closed. The closed mold is then subjected to heat and pressure to cure the cover material thereby forming a cover on the core. With injection molding, compression molding, and casting, the molding cavities typically include a negative dimple pattern to impart a dimple pattern on the cover during the molding process.
Materials previously used as golf ball covers include balata (natural or synthetic), gutta-percha, ionomeric resins (e.g., DuPont""s SURLYN(copyright)), and polyurethanes. Balata is the benchmark cover material with respect to sound (i.e. the sound made when the ball is hit by a golf club) and feel (i.e. the sensation imparted to the golfer when hitting the ball). Natural balata is derived from the Bully Gum tree, while synthetic balata is derived from a petroleum compound. Balata is expensive compared to other cover materials, and golf balls covered with balata tend to have poor durability (i.e. poor cut and shear resistance). Gutta percha is derived from the Malaysian sapodilla tree. A golf ball covered with gutta percha is considered to have a harsh sound and feel as compared to balata covered golf balls.
Ionomeric resins, as compared to balata, are typically less expensive and tend to have good durability. However, golf balls having ionomeric resin covers typically have inferior sound and feel, especially as compared to balata covers.
A golf ball with a polyurethane cover generally has greater durability than a golf ball with a balata cover. The polyurethane covered golf ball generally has a better sound and feel than a golf ball with an ionomeric resin cover. Polyurethanes may be thermoset or thermoplastic. Polyurethanes are formed by reacting a prepolymer with a polyfunctional curing agent, such as a polyamine or a polyol. The polyurethane prepolymer is the reaction product of, for example, a diisocyanate and a polyol such as a polyether or a polyester. Several patents describe the use of polyurethanes in golf balls. However, golf balls with polyurethane covers usually do not have the distance of other golf balls such as those with covers composed of SURLYN(copyright) materials.
Gallagher, U.S. Pat. No. 3,034,791 discloses a polyurethane golf ball cover prepared from the reaction product of poly(tetramethylene ether)glycol and toluene-2,4-diisocyanates (TDI), either pure TDI or an isomeric mixture.
Isaac, U.S. Pat. No. 3,989,568 (xe2x80x9cthe ""568 patent) discloses a polyurethane golf ball cover prepared from prepolymers and curing agents that have different rates of reaction so a partial cure can be made. The ""568 patent explains that xe2x80x9cthe minimum number of reactants is three.xe2x80x9d Specifically, in ""568 patent, two or more polyurethane prepolymers are reacted with at least one curing agent, or at least one polyurethane prepolymer is reacted with two or more curing agents as long as the curing agents have different rates of reaction. The ""568 patent also explains that xe2x80x9c[o]ne of the great advantages of polyurethane covers made in accordance with the instant invention is that they may be made very thin . . . xe2x80x9d, and xe2x80x9c[t]here is no limitation on how thick the cover of the present invention may be but it is generally preferred . . . that the cover is no more than about 0.6 inches in thickness.xe2x80x9d The examples in the ""568 patent only disclose golf balls having covers that are about 0.025 inches thick.
Dusbiber, U.S. Pat. No. 4,123,061 (xe2x80x9cthe ""061 patentxe2x80x9d)discloses a polyurethane golf ball cover prepared from the reaction product of a polyether, a diisocyanate and a curing agent. The ""061 patent discloses that the polyether may be polyalkylene ether glycol or polytetramethylene ether glycol. The ""061 patent also discloses that the diisocyanate may be TDI, 4,4xe2x80x2-diphenylmethane diisocyanate (xe2x80x9cMDIxe2x80x9d), and 3,3xe2x80x2-dimethyl-4,4xe2x80x2-biphenylene diisocyanate (xe2x80x9cTODIxe2x80x9d). Additionally, the ""061 patent discloses that the curing agent may be either a polyol (either tri- or tetra-functional and not di-functional) such as triisopropanol amine (xe2x80x9cTIPAxe2x80x9dor trimethoylol propane (xe2x80x9cTMPxe2x80x9d), or an amine-type having at least two reactive amine groups such as: 3,3xe2x80x2 dichlorobenzidene; 3,3xe2x80x2 dichloro 4,4xe2x80x2 diamino diphenyl methane (xe2x80x9cMOCAxe2x80x9d); N,N,Nxe2x80x2,Nxe2x80x2 tetrakis(2-hydroxy propyl)ethylene diamine; or Uniroyal""s Curalon L which is an aromatic diamine mixture.
Hewitt, et al., U.S. Pat. No. 4,248,432 (xe2x80x9cthe ""432 patentxe2x80x9d) discloses a thermoplastic polyesterurethane golf ball cover formed from a reaction product of a polyester glycol (molecular weight of 800-1500) (aliphatic diol and an aliphatic dicarboxylic acid) with a para-phenylene diisocyanate (xe2x80x9cPPDIxe2x80x9d) or cyclohexane diisocyanate in the substantial absence of curing or crosslinking agents. The ""432 patent teaches against the use of chain extenders in making polyurethanes. The ""432 patent states, xe2x80x9cwhen small amounts of butanediol-1,4 are mixed with a polyester . . . the addition results in polyurethanes that do not have the desired balance of properties to provide good golf ball covers. Similarly, the use of curing or crosslinking agents is not desired . . . xe2x80x9d
Holloway, U.S. Pat. No. 4,349,657 (xe2x80x9cthe ""657 patentxe2x80x9d) discloses a method for preparing polyester urethanes with PPDI by reacting a polyester (e.g. prepared from aliphatic glycols having 2-8 carbons reacted with aliphatic dicarboxylic acids having 4-10 carbons) with a molar excess of PPDI to obtain an isocyanate-terminated polyester urethane (in liquid form and stable at reaction temperatures), and then reacting the polyester urethane with additional polyester. The ""657 patent claims that the benefit of this new process is the fact that a continuous commercial process is possible without stability problems. The ""657 patent further describes a suitable use for the resultant material to be golf ball covers.
Wu, U.S. Pat. No. 5,334,673 (xe2x80x9cthe ""673 patentxe2x80x9d) discloses a polyurethane prepolymer cured with a slow-reacting curing agent selected from slow-reacting polyamine curing agents and difunctional glycols (i.e., 3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,6-toluenediamine, N,Nxe2x80x2-dialkyldiamino diphenyl methane, trimethyleneglycol-di-p-aminobenzoate, polytetramethyleneoxide-di-p-aminobenzoate, 1,4-butanediol, 2,3-butanediol, 2,3-dimethyl-2,3-butanediol, ethylene glycol, and mixtures of the same). The polyurethane prepolymer in the ""673 patent is disclosed as made from a polyol (e.g., polyether, polyester, or polylactone) and a diisocyanate such as MDI or TODI. The polyether polyols disclosed in the ""673 patent are polytetramethylene ether glycol, poly(oxypropylene)glycol, and polybutadiene glycol. The polyester polyols disclosed in the ""673 patent are polyethylene adipate glycol, polyethylene propylene adipate glycol, and polybutylene adipate glycol. The polylactone polyols disclosed in the ""673 patent are diethylene glycol initiated caprolactone, 1,4-butanediol initiated caprolactone, trimethylol propane initiated caprolactone, and neopentyl glycol initiated caprolactone.
Cavallaro, et al., U.S. Pat. No. 5,688,191 discloses a golf ball having core, mantle layer and cover, wherein the mantle layer is either a vulcanized thermoplastic elastomer, functionalized styrene-butadiene elastomer, thermoplastic polyurethane, metallocene polymer or blends of the same and thermoset materials.
Wu, et al., U.S. Pat. No. 5,692,974 discloses golf balls having covers and cores that incorporate urethane ionomers (i.e. using an alkylating agent to introduce ionic interactions in the polyurethane and thereby produce cationic type ionomers).
Sullivan, et al., U.S. Pat. No. 5,803,831 (xe2x80x9cthe ""831 patentxe2x80x9d) discloses a golf ball having a multi-layer cover wherein the inner cover layer has a hardness of at least 65 Shore D and the outer cover layer has a hardness of 55 Shore D or less, and more preferably 48 Shore D or less. The ""831 patent explains that this dual layer construction provides a golf ball having soft feel and high spin on short shots, and good distance and average spin on long shots. The ""831 patent provides that the inner cover layer can be made from high or low acid ionomers such as SURLYN(copyright), ESCOR(copyright) or IOTEK(copyright), or blends of the same, nonionomeric thermoplastic material such as metallocene catalyzed polyolefins or polyamides, polyamide/ionomer blends, polyphenylene ether/ionomer blends, etc., (having a Shore D hardness of at least 60 and a flex modulus of more than 30000 psi), thermoplastic or thermosetting polyurethanes, polyester elastomers (e.g. HYTREL(copyright)), or polyether block amides (e.g. PEBAX(copyright)), or blends of these materials. The ""831 patent also provides that the outer cover layer can be made from soft low modulus (i.e. 1000-10000 psi) material such as low-acid ionomers, ionomeric blends, non-ionomeric thermoplastic or thermosetting materials such as polyolefins, polyurethane (e.g. thermoplastic polyurethanes like TEXIN(copyright), PELETHANE(copyright), and thermoset polyurethanes like those disclosed in Wu, U.S. Pat. No. 5,334,673), polyester elastomer (e.g. HYTREL(copyright)), or polyether block amide (e.g. PEBAX(copyright), or a blend of these materials.
Hebert, et al., U.S. Pat. No. 5,885,172 (xe2x80x9cthe ""172 patentxe2x80x9d) discloses a multilayer golf ball giving a xe2x80x9cprogressive performancexe2x80x9d (i.e. different performance characteristics when struck with different clubs at different head speeds and loft angles) and having an outer cover layer formed of a thermoset material with a thickness of less than 0.05 inches and an inner cover layer formed of a high flexural modulus material. The ""172 patent provides that the outer cover is made from polyurethane ionomers as described in Wu, et al., U.S. Pat. No. 5,692,974, or thermoset polyurethanes such as TDI or methylenebis-(4-cyclohexyl isocyanate) (xe2x80x9cHMDIxe2x80x9d), or a polyol cured with a polyamine (e.g. methylenedianiline (MDA)), or with a trifunctional glycol (e.g., N,N,Nxe2x80x2,Nxe2x80x2-tetrakis(2-hydroxpropyl)ethylenediarnine). The ""172 also provides that the mner cover has a Shore D hardness of 65-80, a flexural modulus of at least about 65,000 psi, and a thickness of about 0.020-0.045 inches. Exemplary materials for the inner cover are ionomers, polyurethanes, polyetheresters (e.g. HYTREL(copyright)), polyetheramides (e.g., PEBAX(copyright), polyesters, dynamically vulcanized elastomers, functionalized styrene-butadiene elastomer, metallocene polymer, blends of these materials, nylon or acrylonitrile-butadiene-styrene copolymer. Wu, U.S. Pat. No. 5,484,870 (xe2x80x9cthe ""870 patentxe2x80x9d) discloses golf balls having covers composed of a polyurea composition. The polyurea composition disclosed in the ""870 patent is a reaction product of an organic isocyanate having at least two functional groups and an organic amine having at least two functional groups. One of the organic isocyanates disclosed by the ""870 patent is PPDI.
Although the prior art has disclosed golf ball covers composed of many different materials, none of these golf balls have proven completely satisfactory. Dissatisfaction, for example, remains with processing and manufacturing the balls, and with the balls"" durability and performance.
Specifically, with respect to processing, prior materials are not user friendly because certain starting materials may be unhealthful, such as diamines and isocyanides. In addition, prior balls using such materials are generally wound balls. Wound balls have tolerances that are more difficult to control due to core sizes and/or windings sizes, and therefore, require thicker cover layers to account for the manufacturing tolerances. With respect to durability problems, prior polyurethane covered balls, because they are wound balls, tend to lose compression and initial velocity due to the windings relaxing over time and use. With respect to performance problems, prior balls, as a general rule, tend to have smaller cores that result in shorter flight distances. Although many golf balls having a polyurethane cover have been provided by the prior art, these golf balls have failed to capture the sound and feel of balata while providing a golf ball with the durability of an ionomer.
The present invention provides a golf ball that demonstrates the best overall durability and distance as yet put forth by the golf industry while adhering to all of the rules for golf balls as set forth by the USGA and The Royal and Ancient Golf Club of Saint Andrews. The golf ball of the present invention is able to accomplish this by providing a cover composed of a blend of polyurethane prepolymers.
One aspect of the present invention is a golf ball that includes a core and a polyurethane cover formed from reactants including a toluene diisocyanate based polyurethane prepolymer, a second diisocyanate polyurethane prepolymer and at least one curing agent. The toluene diisocyanate based polyurethane prepolymer of the golf ball may include toluene diisocyanate and polyether polyol. The golf ball may include at least one boundary layer disposed between the core and the polyurethane cover. The second diisocyanate polyurethane prepolymer of the golf ball is different from the toluene diisocyanate based polyurethane prepolymer and may be a p-phenylene diisocyanate based polyurethane prepolymer. The p-phenylene diisocyanate based polyurethane prepolymer may include p-phenylene diisocyanate and one or more polyester polyols, polyether polyols or a mixture thereof. The p-phenylene diisocyanate based polyurethane prepolymer of the golf ball may include p-phenylene diisocyanate and polycaprolactone polyol.
Another aspect of the present invention is golf ball including a core, a boundary layer and a thermoset polyurethane cover. The core includes a polybutadiene. The boundary layer encompasses the core and includes at least one ionomer. The boundary layer has a shore D hardness in the range of 50 to 70. The thermoset polyurethane cover encompasses the boundary layer. The thermoset polyurethane cover has a Shore D hardness in the range of 40 to 55, and a thickness in the range of 0.02 to 0.05 inches. The golf ball has a durability of at least 3.5 on a scale of 1 to 5 based on a cover shear test.
The golf ball may have the thermoset polyurethane cover formed from a p-phenylene diisocyanate terminated polyether prepolymer, a toluene diisocyanate terminated polyether prepolymer and at least one other component. Alternatively, the golf ball may have the thermoset polyurethane cover formed from a p-phenylene diisocyanate terminated polyester prepolymer, a toluene diisocyanate terminated polyether prepolymer and at least one other component. Yet further, the golf ball may have the thermoset polyurethane cover formed from a p-phenylene diisocyanate terminated polyether prepolymer, a p-phenylene diisocyanate terminated polyester prepolymer, a toluene diisocyanate terminated polyether prepolymer and at least one other component. The at least one other component may be a blend of a diamine curing agent and a diol curing agent.
Yet another aspect of the present invention is a golf ball including a core, a boundary layer and a polyurethane cover formed from 0 to 90 parts of a p-phenylene diisocyanate terminated polyester prepolymer, 0 to 90 parts of a p-phenylene diisocyanate terminated polyether prepolymer, 10 to 40 parts of a toluene diisocyanate polyurethane prepolymer, and at least one curing agent. The at least one curing agent may be a blend of a diamine curing agent and a diol curing agent. More specifically, the diamine curing agent may be diethyl 2,4-toluenediamine, and the diol curing agent may be a 1,4 butane diol and glycol.
The polyurethane cover may have a hardness of between about 45-60 Shore D, a flexural modulus of between about 12,000-35,000 psi, a Bayshore resilience of between about 50-70, and a tensile strength of between about 5900-7500 psi. More specifically, the polyurethane cover may be formed from 20 parts of a p-phenylene diisocyanate terminated polyester prepolymer, 50 parts of a p-phenylene diisocyanate terminated polyether prepolymer, and 30 parts of a toluene diisocyanate polyurethane prepolymer. Alternatively, the polyurethane cover may be formed from 70 to 80 parts of a p-phenylene diisocyanate terminated polyether prepolymer, and 30 to 20 parts of a toluene diisocyanate polyurethane prepolymer.
Yet another aspect of the present invention is a method of fabricating a golf ball. The method generally includes cast molding a polyurethane cover over a golf ball precursor product. The golf ball precursor product may be a core, or a core and boundary layer. The polyurethane cover is formed from a toluene diisocyanate based polyurethane prepolymer, a second diisocyanate based polyurethane prepolymer and an agent. The agent is selected from the group consisting of a curative, a chain extender, a cross-linking agent and a mixture thereof.
The method may also include heating the tolune diisocyanate based polyurethane prepolymer and second diisocyanate based polyurethane prepolymer to a predetermined temperature. The method may also include heating the agent to a predetermined temperature. The method may also include mixing the toluene diisocyanate based polyurethane prepolymer and second diisocyanate based polyurethane prepolymer with the agent to form a common mixture prior to cast molding the cover over the golf ball precursor product.
The cast molding step may include placing the golf ball precursor product in a first half of a mold containing the mixture of toluene diisocyanate based polyurethane prepolymer, the second diisocyanate based polyurethane prepolymer and the agent. The cast molding step may also include curing the mixture of toluene diisocyanate based polyurethane prepolymer, the second diisocyanate based polyurethane prepolymer and the agent for a predetermined time period. The cast molding step may also include mating the first half of the mold with a second half of the mold. The second half of the mold would contain the mixture of toluene diisocyanate based polyurethane prepolymer, the second diisocyanate based polyurethane prepolymer and the agent. The cast molding step may also include pressing the first half of the mold and the second half of the mold together for a predetermined time period.
The method may include adding a third diisocyanate based polyurethane prepolymer to the prepolymer mixture. The second diisocyanate based polyurethane prepolymer may be a p-phenylene terminated polyether prepolymer and the third diisocyanate based polyurethane prepolymer may be a p-phenylene terminated polyester prepolymer.
Another aspect of the present invention is a polyurethane system. The polyurethane system is formed from reactants comprising 0 to 90 parts of a p-phenylene diisocyanate terminated polyester prepolymer, 0 to 90 parts of a p-phenylene diisocyanate terminated polyether prepolymer, 10 to 40 parts of a toluene diisocyanate polyurethane prepolymer, and at least one curing agent.
Another aspect of the present invention is a method for forming a polyurethane system. The method includes blending a tolune diisocyanate based polyurethane prepolymer with a second diisocyanate based polyurethane prepolymer to form a polyurethane prepolymer blend. The method also includes heating the prepolymer blend to a predetermined temperature, and then mixing the polyurethane prepolymer blend with a curing agent to form the polyurethane system.